Process for breaking petroleum emulsions



Patented July 1, 1952 PROCESS FOR BREAKING PETRQLEUM EMULSIONS Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, Ltd, Wilmington, Del., a corporation of Delaware N Drawing. Application September 5, 1950, Serial No. 183,293

Claims. 1

This invention relates to petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

One object of my invention is to provide a novel process for breaking or resolving emulsions of the kind referred to.

Another object of my invention is to provide an economical and rapid process for separating emulsions which have been prepared under controlled conditionsirom mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned, are of significant value in removing impurities particularly inorganic salts from pipeline oil.

Demulsification as contemplated in the present application includes the preventive step of commingling the demulsifier with the aqueous component which would or might subsequently become either phase of the emulsion, in absence of such precautionary measure. demulsifier may be mixed with the hydrocarbon component.

The demulsifying agent employed in the present process is a fractional ester obtained from a polycarboxy acid and a diol obtained by the oxypropylation of dihydroxylated ethers of glycerol with the proviso that each ether radical of the original glycerol diether have less than 8 carbon atoms and is preferably obtained from awatersoluble aliphatic alcohol but may be obtained from an alicyclic alcohol such as cyclohexanol or from a phenol such as hydroxybenzene or cresol. Glycerol ethers which have two ether linkages and also two hydroxyl radicals and a lengthy repetitious polypropylene oxide radical in the form of a polyether are suitable for the synthesis which yields the herein described demulsifying agents. Such ethers can be obtained by various procedures. The simplest procedure is to obtain diethers of glycerol and react such diether with a plurality of moles of propylene oxide and subsequently convert such monohydric compound into a diol by means of glycide. A number of diethers of glycerol, such as glycerol alphagamma diisopropyl ether, glycerol alpha-gamma diphenyl ether, etc., are available in the open market. These products are prepared readily by reacting. epichlorohydrin with the selected alcohol so as to yield an ether of epichlorohydrin.

Similarly, such Such ether can then be reacted with, alkali so as to give a glycidyl ether. Such glycidyl ether can be reacted further with a second mole of alcohol, either the same alcohol or a diiferent alcohol, so as to yield a diether of glycerol. As to a complete description of such reaction see pamphlet entitled Epichlorohydrin, Shell Chemical Corporation, 500 Fifth Avenue, New York city, N. Y.

More specifically then the glycerol 'diethers are obtained from hydroxylated compounds such as an alcohol, phenol, or phenoxylalkanol or the like, free from any radical having 8 or more carbon atoms. Such monohydric glycerol diether is reacted with propylene oxide so as to obtain a high molal alcohol ether or glycerol diether. The monohydric compound so obtained is reacted with glycide so as to get a diol in which both hydroxyls are attached to two of the three terminal carbon atoms at one end of the molecule, and at the other end of the molecule there is a branched structure due to the fact that a diether of glycerol was the initial starting material. All of this will be described more fully subsequently.

Reference is made to the fact that the initial monchydric reactant used to produce the diether of glycerol must have less than 8 carbon atoms. This means that the oxypropylated monohydric compound must be free from any radical having 8 carbon atoms or more. Such compound is in essence a high molal ether alcohol. The expression high molal is employed to indicate a product having a molecular weight from 1,000 to several thousands, preferably within the range of 1,500 to 4,000 or even a more narrow range as stated subsequently. Suitable monohydric materials include the usual aliphatic alcohols, such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, allyl alcohol, hexyl alcohol, etc. Also there are included the phenols such as hydroxybenzene and cresol. Similarl the hydrogenated derivatives of such phenols, i. e., the alicyclic alcohols, are included. Benzyl alcohol and hydrogenated benzyl alcohol may be used. Other alcohols which can be employed include tetrahydropyran-2-methanol and tetrahydrofurfuryl alcohol. My preference is to use aliphatic alcohols having at least 3 carbon atoms and preferably being water-soluble. This includes propyl alcohol, butyl alcohol, or amyl alcohol. In the case of butyl and amyl alcohols some of the isomers are water-soluble to the extent that they show solubility to the extent of a few percent at room tempereature. Reference to the hydrocarbon group of such alcohols includes, of course, the derivatives of tetrahydropyran-Z-methanol 3' and tetrahydrofurfuryl alcohol even though there is an oxygen atom present. For the present purpose such radicals act as if they were entirely hydrocarbon in nature insofar that the presence of the oxygen atom contributes no objectionable property.

The oxypropylation, or for that matter the treatment of such monohydric compounds with any alkylene oxide and particularly ethylene oxide and propylene oxide, is well known. It is preferably conducted in the presence of an alkaline catalyst and a residual catalyst is preferably permitted to remain'in the mass at the end of the reaction in order to catalyze" subsequent treatment with glycide.

Briefly stated then a monohydric alcohol or other monohydric reactant having less than 8 carbon atoms in any single radical may be indicated thus: ROH. Such reactant can be employed to produce a diether of glycerol which, for convenience, canbeindicated thus:

Reacting such monohydric alcohol, or more correctlymonohydric ether alcohol, with propylene oxide the resultant ether alcohol may be indicated thus:

It has been pointed out previously that such monohydric ether alcohols must be of fairly high molecular weight and thus the value of n in the precedin formula is within the range of approximately to 80. My preference is that the molecular weight-of the compound at this stage, i. e., prior to treatment with-glycide, be within the range of 2,000 to 3,000. Purely as a matter of convenience the preceding formula can be rewritten thus:

"oansow'ammflosmon R'o without changing n to 11-1.

Itis immaterial as to the method-of obtaining the diethers of glycerol and as to the method of oxypropylating such compounds. Oxypropylation is conventionally conducted in presence of an alkaline catalyst such as caustic soda, sodium methylate, etc.

Having obtained such high molal oxypropylated derivative it is'then treated with glycide or otherwise reacted so as to produce a diol which also may be referred to for convenience as an etherized glycerol. This may be shown in the following reaction:

imowimoncgmona onion-on on. RO

In examining the above reaction it is obvious that an isomeric mixture is obtained for reasons which are obvious in light of what is said subsequently concerning oxyethylation or o'xypropylation when there is a multiplicity of recurring alkylene oxide units. Furthermore, propylene oxide being an unsymmetrical alpha-beta oxide it may have ring rupture so as to involve, at least theoretically, twodifferent isomeric derivatives. This is true, also, in regard to glycide, i. e., at

least theoretically as the'two terminal"=hydroxyls,

instead of'being'a-ttached tothe two carbon atoms shown, might be attached to the first and second carbon atoms and not to the third, or more correctly the branched chain carbon atom.

From what is said hereinafter it is immaterial as to which particular isomer is obtained, or if a mixture isobtained. In any event, having obtained suchglycol ether or diol, or etherized glycerol, such product is then reacted with a polycarboxy acid 'or anhydride in the ratio of two: moles of acid or anhydride for each mole of diol.

Briefly then, the present invention is concerned with a process for breaking petroleum emulsions of the water-in-oil typecharacterized-by subjecti-ng the emulsion to the action of a demulsi fier including hydrophile synthetic products; saidh-y'drophilesynthetic products being characterized by the following formula:

in which n is a whole number-varying from 15" to n" is a whole number not over- 2'; Ris a hydrocarbon radical having less than 8 carbon atoms; and R, is a radical of thepolycarboxy'acid (30011 \c 0011). in which n" has its previoussigni'ficance; with the further proviso that'thep'arent' diolprior to esterification be water-insoluble and kerosenesoluble, and furthermore that in said diol the two hydroxyl radicals be attached to two of 'thetliree adjacent carbon atoms of aterminal group 'opposite to the terminal group Attention is-directed to the co-pendingapplication of C. M. Blair, Jr., serial No. 70,811, filed January 13, 1949' (now Patent No; 2,562,878,'dated Aug. 7, 1951) inwhi'ch'there isd'escribedamong other things, a' process forbre'aking petroleum emulsions of the Water-in oil type characterized by subjecting the emulsionto the -action 'ofa'n esterfication-productof a dicarboxylic acid and a polyalkylene glycol in which the ratio "of equivalents ofpolyba'sic acid to equivalents of polya'lkylene glycol is intherange-of 0.5 to 2.0, in which the alkylenegroup has. from 2 to 3 carbon atoms, and in which the molecular weight of'the product isbetween 1,500 to 4,000.

Similarly, there have been-used esters'o'f die carboxy acids and polypropylene glycols in which 2 moles of the'dicar'boxy acid ester have been'reacted with onemole of apolypropylene glycol having a molecularweight, for example, of- 2g000 so as to form an acidic fractional ester. Examination of what is said subsequently herein as well as the hereto appended claimsin comparison with the previous example will show the line of delineation between such somewhat comparable compounds. Of greater significance, however, is

what is said subsequently in regard to the structure of the parent diol ascomparedto polypropylene glycols whose molecular weights may vary from1,000 to 2,000.. i

For convenience, what is said hereinafter may be divided into six parts:

Part 1 will be concerned with the oxypropylation derivatives of the monohydric compounds;

Part 2 will be concerned with the preparation of: the diols by reacting the above-mentioned tained by modest oxyethylation preceding the oxypropylation step, or oxypropylation followed by oxyethylation. Similarly, modest oxypropylation could follow treatment-with glycide. This resultsin diols having somewhat difierent properties which can then be reacted with the same polycarboxy acids or anhydrides described in Part 3 to give efiective demsulifying agents. For this reason a description of the apparatus makes casual mention of oxyethylation. For the same reason there is brief mention of the use of glycide.

- PART 1 Previous reference has been made to the use of certain monohydric compounds as initial raw materials. Such compounds include glycerol alpha-gamma dirnethyl ether, glycerol alphagamma diethyl ether, glycerol alpha-gamma diisopropyl ether, glycerol alpha-gamma dibutyl ether, glycerol alpha-gamma diphenyl ether, etc. As a matter'ofconvenience, the invention will be illustrated by means of the two raw materials most readily available, i. e., glycerol alpha-gamma diisoproyl ether and glycerol alpha-gamma di- For a number of well known reasons equipment, whether laboratory size, semi-pilot plant size; pilot plantsize, or large scale size, is not as a rulejdesignedfor a particular alkylene oxide. Invariably. and inevitably, however, or

particularly in the case of laboratory equip.

ment and pilot plant size the design is such as to use any of the customarily available alkylene oxide, i. e., ethylene oxide, propylene oxide, butylene oxide, glycide, epichlorohydrin, styrene oxide, etc; In the subsequent description of the equipment it becomes obvious that it is adapted for oxyethylation as well as oxypropylation.

Oxypropylations are conducted under a wide variety of conditions, not only in regard to presence or absenceof catalyst, and the kind of catalyst, but also in regard to the time of reaction, temperature of reaction, speed of'reaction, pressure during reaction, etc. For instance, oxyalkylations can be conducted at temperatures up to approximately 200 C. with pressures in about the same range up to about 200 pounds per square inch; They can be conducted also at temperatures approximating the boiling point of water or slightlyabove, as for example 95 to 120 o: Under such "circumstances the pressure I Us will be less than 30 pounds per square inch un- 1essi some special'procedure is employed as is sometimes the case, to wit, keeping an atmosphereof inert gas such as nitrogen in the vessel during the reaction. Such low-temperature-low reaction rate oxypropylations have been described very completely in U. S. Patent No. 2,448,664, to H. R. Fife, et al., dated September 77,1948. Low temperature, low pressure oxy pr'opylations are particularly desirable where the compound being subjected to oxypropylation contains'one, two or three points of reaction only, such as monohydric alcohols, glycols and triols.

" Since low pressure low temperature reaction speed oxypropylations require considerable time, for instance, 1 to 7 days of 24 hours each to complete the reaction they are conducted as a rule whether ona laboratory scale, pilot plant scale, or large 'scale, so as to operate automatically. The prior figure of seven days applies especially to large-scale operations. I have used conventional equipment with two added automatic features; (a) a solenoid controlled valve which shuts off the propylene oxide in event that the temperature gets outside a predetermined and set range, for instance, to 0., and (b) anothersolenoid valve which shuts ofi the propylene oxide (or forthat matter ethylene oxide if it is being used) if the pressure gets beyond a predetermined range, such as 25 to =35 pounds. Otherwise, the equipment is substantially the sameas is commonly employed for this purpose where the pressure of reaction is higher, speed of reaction is higher, and time of reaction is much shorter. In such instances such automatic controls are not necessarily used.

Thus, in preparing the various examples I have found it particularly advantageous to use laboratory equipment or pilot plant which is designed to permit continuous oxyalkylation whether it be oxypropylation or oxyethylation. With certain obvious changes the equipment can be used also to permit oxyalkylation involving the use of glycide where no pressure is involved except the vapor pressure of a solvent, if any, which may have been used as a diluent. 7

As previously pointed out the method of using propylene oxide is the same as ethylene oxide. This point is emphasized only for the reason that the apparatus is so designed and constructed as ,to use either oxide.

The oxypropylation procedure employed in the preparationof the oxyalkylated derivatives has beenuniformly the same, particularly in light of the'fact that a continuous automatically-controlled procedure was employed. In this procedure the autoclave was a conventional autoclave made of stainless steel and having a capacity of approximately 15 gallons and a working pressure .of one. thousand pounds gauge pressure. This pressure obviously is far beyond any requirement as far as propylene oxide goes unless there is a reaction of explosive violence involved due to accident. The autoclave was equipped with the conventional'devices and openings, such as the variable-speed stirrer operating at speeds from 50 R. P. M. to 500 R. P. ML; thermometer well and thermocouple for mechanical thermometer; emptying outlet; pressure gauge, manual vent line; charge hole for initial reactants; at least one connection for introducing the alkylene oxide, such as propylene oxide or ethylene oxide, to the bottom of the autoclave; along with suitable devices for both cooling and heatingthe 7 autoclave; suchas a cooling jacketrand'; prefers ably; coils addition 'theretoi'w'ith' the 'ij'acket so"'arrangedthatjit. is suitable for' heating with steam or cooling-with water'and further equipped with electrical heating devices. 4 Such autoclaves are, of course; 'in' essence "small-scale replic'as'of the usual conventional. autoclave usedin oxyalkylation' procedures. In someinstancesin-exploratory preparations arr autoclavehaving a'smaller capacity; for instance; approximatelye /z liters in one-case and "about 1% gallons in-anoth'er case,-was-used.

Continuous Operation; or-substantially continuous operation, was achieved by the use-ofa separate container to hold' 'the'; -a'lkylene-- oxide being employed;--particularlypropylene cxide. "In conjunctionwith the smallerautoclaves; the container consists-essentia1lyor a-labora-tOry bomb having a capacityofabout one-half gallomor somewhat in excess the'reof.' In someinstances a-larger bombwas used; to --*wit,-'-one having a capacity-ofabout one- -gallon. 'Ihis-bomb -was equipped,- also; with an-' inlet=-for charginsr-and an 'eductor tubegoingtothe bottom of the containerso as to=-permit dischargingof -alkylene oxide in the liquid phase to' the-autoclave. *A bomb having a-capacity of about 60 pounds was used in connection with the--15-gallon-autoclave. Other conventional equipment consists; of course, of the rupture disc, pressure'gauge;=-sight feed glass, thermometer connection for nitrogen mr pressuring bomb, etc. ""The bomb was placed on a scale during-usei I-he connections-betweenthe bomb and the autoclave were-l-fleirible stainless steel-hose ortubing so that continuous weighings could be made without breaking orm-akingany connections. This appl-ies=-alsoto the nitrogen line. which was used t'o pressure-thebombreserv o'ir. I To l the "extent that-it was req'uiredpany other: usual 7 conventional procedure or "addition whichprovided greater-'safetywa's-used', ofco'urse, such as safety glass'protective's'creensetc.

. Attention is directed-. again to what has -been said previously in regardto automatic" controls which: shut off' the propylene ox'ide in eve'nt temperature of reaction passes out or the predetermined range or if pressurein the autoclave passes 'o'ut ofpredetermined range.

I 7 With- 'this p'articular arr'angement' practically all ox-ypropylationsi become uniform in that -the reaction temperaturewas-held w ithin a=*few degrees of any selected point, for-instancegif 105 C. was selected as the operating:temperature-- the maximum point'would-be I at themost "110 C. or 112 (3., and the-l0wer-pointwou1d.=b 95 0r possibly 98 C.- Similarlythe pressure was held at approximatelyJ30 pounds' within a- -5-p0und variation one-wayor the other, but mightdrop to practically zero; especially 1 where no ''solvent such as xylene is employed. The speed'of reaction' was comparativelyslow- -under "such conditions as compared with oxya1kylationsat200 C. Numerous reactions: were conducted'in which-the time". varied from one J day "(24 hours): up to three days "(-72 hours) "iorT'completiou "of "the" final m'emberof a's'e'ries. I'n' someinstances the'reaction may "take place in considerably less time, 1. e124 hours 'or less; as far as a partial "oxypropylation is concerned;'Theminimumtime recorded" was about; a 3-hour p'erio'din' a single step. Reactions indicated as being complete in IO hOursmay .haVeFbeen complete. in a lesser period I of. time in light .ofltheautomatic equipment employed. This. applies I also. where the reactions were complete in a shorter 'period'of timaior instance; 4 to 5"h'ours; "In theaddition of propylene oxide;'"in*' the autoclave equipment as far 'as possible the valves were set so all-the propylene oxide if fed continuously "would; 'be added-"at a' rate so that j the-predetermined amount would react within thefirst '15- hours of the "24-hour periodortwo-thirds of any" shorter period. *Thismeant that if-the reaction-was interrupt'ed" automatically for aperi'odof time for pressure to drop'or temperature to dropthe-predetermined amount of oxide "would stilllee-added in most instances well-within-t-he predetermined time period. j Sometimes where-the addition was a comparatively smalram'ountin a10-hour period therewould be amunquestionable -speeding up=of the re"action, "by simply" repeating the-examples and using 3 4', or 5 hours-insteador 10* hours.

"When" operating at-a' comparativelyhigh-temperature; for instance," betweeni'EO" revenu 0., an unreacted alkylene oxide suchas'propylene oxide, makes its presence *felt in-the"inc're'ase'in pressure-or the consistency "of a higher pressure. However, at a low enough-tempe'ratureit may happen: that the propyleneoxide-goesin as a liquid. Ifso; and if" it-remains unreacted -there is; of course'rari-inlrerent dangerandappropriate steps =must- "be taken to" safeguard against "this possibility; "if 'need'mea sample-must'be withdrawnand examinedforunreactedh propylene oxide. (me-"obvious 'pro'ce'clurey-of course, is-to oxypropylate at I a modestly higher temperature, for instance, at 14 0"t'o'-'-150"C. Unreacted-oxide affects 1 determinationof the acetyl or 'hydroxyl value 'of the hydroxy'lat'ed "compound obtained.

"The higher the molecularweight ofthe'c'ompound, i. e., towards the-latter stages of reaction, the longer the time .required to. add a given amount of "oxide. One" 'p'jossibl'e explanation' is that "the" molecule; being la'r'gerjthe opportunity for random reaction' isdecreased. 'Inverselygthe lower the mol'ecular weight the 'faster'f'the reaction takes place. For this reason; sometimes at least-increasing the 'conc'entrationof thecataly'st does not appreciably speed up theireacti'on; particularly when'the' product subjected to oxyalkylation ,'has a comparatively high molecular weight; However; as has been pointed out previ'ouslyy'operating at-- a *1owpr'essure and: a'low temperature even in .large scale .opierationsl as much as a" week or Item 'days' time may. lapse'to obtain some of the higher molecular" weight derivatives from-*moriohydric.ori'dihydric materials.

In a number of 'operations the counterbalance scaleor dial *scaletholding" the'pr'opyl'ene oxide bomb" was subset that when the j predeterm'ined amount of propylene oxide had' passed 'intol the reaction 'the scalemovement through a time operating device"was-- set for {either one to two hours "so that reaction continued-for 1 1563 hours after the; final addition 'ofith'. last .probylene oxide'andtherea'fter theoper'ation was .sliutldown. This particuland'evice. is. particular-1y.suitable for use. on larger equipment. than. laboratory size autoclaves, to wit, on semi-pilotlplant-orwpilot p'lants'ize. as well. asv on large .scalesize. 1 This final stirring. periodis Jintended toavoid the presence of unreacted' oxide.

Irf'this sort. ofoperation, of course,. .the-temperature-range;.was contrblled. automatically by either useof. cooling water,isteam, or electrical heat',"'.'s0 "astofir'aise' or lowerthe-I temperature. The: pressuringof "the propylene .oxideinto. the reaction-vessel was also automatic .iinsofari. that v the 'feedj strejamjwas"setifon aslow...continuous run whichwas sl'iutoff'in case the pressure passed a predetermined point as previously set out. All the points of design, construction, etc., were conventional including the gases, check valves and entire equipment. As far as I am aware at least two firms, and possibly three, specialize in autoclave equipment such as I have employed in the laboratory. and are prepared to furnish equipment of this same kind." Similarly pilot plant equipment is available.- This point is simply made as a precaution in the direction of safety. Oxyalkylations, particularly involving ethylene oxide, glycide, propylene oxide, etc., should not be conducted except in equipment specifically designed for the purpose.

Example 111 The monohydric compound employed was glycerol alpha-gamma diisopropyl ether. The product was substantially anhydrous. In the initial oxypropylation this material was reacted with propylene oxide in the ratio of 20 moles of propylene oxide for each mole of the monohydric ether alcohol. Theautoclave employed was one having a capacity of about gallons, or approximately 40 pounds of reaction mass. The speed of the stirrer could be varied from 150 to 350 R. P. M. 3.52 pounds of glycerol alpha-gamma diisopropyl ether was charged into the autoclave along with 7 ounces of sodium hydroxide. The reaction pot was flushed out with nitrogen. The autoclave was sealed and the automatic devices set for injecting 23.2 pounds of propylene oxide in 3 hours, with an allowance of another hour for stirring to insure completeness of reaction. The pressure regulator Was set for a maximum of 35 pounds per square inch. This meant that the bulk of the reaction could take place, and probably did take place, at a comparatively lower pressure. This comparatively low pressure was the result of the fact that considerable catalyst was present. The propylene oxide was added at the rate of about 8 pounds per hour. More important, the selected temperature range was 205 to 215F. (about the boiling point of water). The initial introduction of propylene oxide was not started until the heating devices had raised the temperature to about the boiling point of water. At the completion of the reaction the molecular weight, based on hydroxyl determination, was 820 compared with a theoretical molecular weight of 1336.

The final product was fairly water-soluble and fairly dispersible in xylene but not soluble in kerosene, or at least the bulk of the compound was not soluble in kerosene.

This batch of approximately 27 pounds was divided into five equal. portions and subsequently subjected to further'oxypropylation as described in Examples 2a to 6:1, inclusive.

Example 2a In this instance the same procedure was employed as in Examplela; preceding, except that the initial reactant was 5.3 pounds of the oxypropylated derivative described as Example 1a, preceding. To this mixture there was added 3 /2 ounces of caustic soda. The time period was about 1% hours with an added 45 minutes for stirring. The amount of oxide added was 5.3 pounds. The molecular weight, based on hydroxyl value, was 1075 compared with a theoretical molecular weight of 2496.

The conditions of temperature and pressure were substantially the same as in Example 1a, p e he p oduct was Water-insoluble.

xylene-soluble and kerosene-soluble. This statement applies also to the next four examples and will not be repeated.

Incidentally, the appearance of all these prod- I ucts varied from rather viscous, colorless or straw-colored compounds to others having an amber tint. Those of the highest molecular weight'would hardly flow at ordinary temperature or at least were rather viscous.- Foi convenience,I have stored samples in wide-mouth cans. This applies to all the various samples herein described and this statement will not be repeated. Also, what is said in regard to color and Viscosity applies'to samples after treatment with glycide as described in Part 2.

Example 3a The same procedure was followed as in Example 2a, preceding, i. e., the initial charge was 5.3 poundsof the product identified as Example 1a, preceding. The amount of propylene oxide added was 9.3 pounds. The amount of catalyst added was 5 ounces. The time period for the addition of propylene oxide was 1% hours with another hour for stirring to insure completeness of reaction. The final product showed a molecular weight, based on hydroxyl value, of 1485 compared with theoretical molecular weight of 3656.

The conditions of temperature and pressure were all the same as in the previous examples and, as a matter of fact, applied to all the subsequent examples in this series, i. e., Examples 4a through 611, so this information Will not be repeated.

Example 4a The initial reactant was the same as in the two Example 5a The same procedure was followed as in Ex amples 2a, 3a, and 4a, preceding. The initial reactant was 5.3 pounds of the material previously identified as Example la, preceding. The amount of propylene oxide added was 18.6 pounds. The

amount of catalyst added was 7.5 ounces of caustic soda. The time period. for the introduction of the oxide was 3 hours and the reaction mass was stirred for an hour longer to insure completeness of reaction.

The final product showed a molecular weight based on hydroxyl number of 2230 compared with a theoretical molecular weight of 5976.

Example 612 The same procedure was followed as in Example 5a, preceding. The initial reactant as before 5.3 pounds of the product identified as Example la, preceding. The amountof propylene.

h same procedure was employed inv connection withglycerol alpha-gamma di-phenyl ether. The characteristics of the product-were much the same exceptthat the tendency for water-solubility ;to= decreas.eyand for xylene-solubility and kerosene-solubility to increase in the earlier stages pounds of-glycerol alpha-gamma .diisopropyl:

other; 'I'heini-tial reaction masswas broken into five parts of. approximately 5.6 pounds-v each in.- stead of 5.3. pounds each.- The amount of oxide added;the.-time factor,-ternperature factor, p1es' surefactor; etc, were substantially the :same within-ability to repeat thesecond series as. in mples wthr u h'fia- Although-caustic soda. was used in the above oxypropylation needless to say any other suitable catalyst, such as sodium methylate, caustic potash, or the like,-could1 have been employed equally. satisfactorily.

Speaking ofjnsolubility in water or solubility.

in kerosene suclrsolubility test can be. made. simply by shaking'small amounts. of the. materials.

ina test tube with water, for. instance,.using.1%. to %.approximately based ,on. the. amount, of, ter present,

Needless to say, there is no completeconversion of" propylene. oxide into the. desired hydroxylated compounds. the theoretical molecular weight-based on. a statistical average .is. greater than. the. molecular 1 weight calculated by. .usual vmethods onbasis of acetyl or hydroxyl value. Actually, there is no completely satisfactory method for determining molecular weights of thesetypes of ,compounds witha high degreaof accuracywhen the molecular weightsiexceedmoo or 20.0.0; Insome Lin.-

stances-the acetylvalue 0r hydroxyl value serves as satisfactorily as an'indexto the molecular weight :as. any other procedure, subject to the above limitatio-na-and especially in the higher. molecular :weight range. If any'diihculty is encountered in theimanufacture of the esters as described .inPart 3 the stoichiometrical amount of acidr'orsacid. compound should .be taken which This is indicated by ,thefact. that.

correspondseto. the::.indicated;;acety1 or r oxyl value. This :matternhasvbe n isc ssed in th literaturaandisia mattereor commonrk e se andvrequiresano:furth r e aboration In fact, i i illustratedr byrsome oiwthe examp esap ea ncin.

the natentprevi usly-m ntioned:

Paar-2 its-pr vi usly stat t e pr pylat' d' m no-- hydricteompounds of comparatively high-molecular'weight (usually in excess of '1,000'-'basedon .hydroxyl value); are converted into -diolsf reaction with glycide mole for mole. vNeedless to say, other reactions can be employed which do not involve glycide,-.-for.-example, one can produce. .ethers of thekind herein employed. by useof. a ly erol.monochloroh dri '6', ei alpha .01 ,beta lycerol. Imonochlorohydrin. Attention isdireoted; again. to the fact that in the previous formula ,andxin the formulas in the claimsit would. be immaterial whether the free hydrox l, .radicals prior to esterification are present as attached .to the firstand third terminal carbon atoms, or second and third carbon atoms. This is, simply an isomeric difference depending .on how-the epoxy ring is ruptured in the case of glycide; or. whether one employsglycerol alpha monochlorohydrin.

Other suitableprocedure involves the use of epichlorohydrin in a conventional manner; For

instance, the 'oxypropylated compound can'be treated-- with,-.epichlorohydrin and the resultantproduct-treated withcaustic soda so as to reform the epoxy-ring; The epoxide so obtained canthen be treated with water'so as to yield a compound having-two hydroxyl radicals attachedto two of. the three terminally adjacent carbon atoms.

Attention-isdi-rected to the fact that the use of glycide requires-extreme-caution. This is particularly true on any scale other than small laboratory or semi-pilot'plant operations. Purely from the standpoint of safety in the handling of glycide, attentionisdirected tothe following: (a) If prepared from glycerol monochlorohydrin, this product should be comparatively pure; (b) the glycide itself should be as pure as possible as the effect ofyimpuritiesisdifficult to evaluate; (c) the glycide should be introduced carefully and precaution should be taken that it reacts as promptly as introduced, i. e., that no excess of glycideisallowed to accumulate; (d) all necessary precaution should be taken that glycide cannot polymerize per se;- (6) due to the high' an .added .lopeningatxthe top the. glass resin pot. or comparahlef vessel should be equipped with a stainless steel cooling coilso that the pot can be cooled 'morerapidly than mere removal of themantle; If a. stainless steel-coil is introduced it means thatthe conventionaL stirrer of the.

paddle type ischanged into thecentrifugal type which'causes the fluid. o1" reactants-to mix vdue to swirling action in the center of the pot. Still better, is the use ofca-1aboratoryautoclave of the kindpreviously described in Part 1; but in any event; when the initialwamount of .glycide' is added to a suitable reactant, such as Examples 2a through 6a, preceding, the speed of reaction should be controlled by the usual factors, such as (a) the addition of glycide; (b) the elimination of external heat; and (c) the use of a cooling coil so there is no undue rise in temperature. All the foregoing is merely conventional but is included due to the hazard in handling glycide.

Example 1b The equipment used was the glass resin pot of the kind described above. Into this pot were charged 165 grams of the product identified as Example 1a, preceding. To it there was added 1% sodium methylate. There was additional alkaline catalyst present due to the caustic used in the preceding oxypropylation. Thetemperature of the reaction mass wasraised to about 120 C. 15 grams of glycide was added in a period of a little over an hour. Whenever the temperature tended to rise past 130 C. the reaction mass was cooled. If the temperature showed a tendency to drop below 112 to 115 C. the reaction mass was heated. When all the glycide had been added the reaction mass was stirred for approximately an hour longer at 130 C. and then heated to a temperature below the decomposition point of glycide, for instance, 140 C., and held at this temperature for another hour. In this particular reaction there is less hazard than is usually the case insofar that the amount of glycide added was comparatively small. Even so, such oxyalkylation should be conducted with extreme care. 1

These data and similar data are summarized in the following table.

TABLE 2 M01. Wt.

Amt. of Ex. Ex. l\o. of M01210" Mono- Gly- 1 of hydrrc D101. Ob- N o. Monohydnc cide Compound tamed Galof hydnc Ba ed on Compound Amt. culat d f 0m Diol Compound H Used (grs.) e r ydroxyl rs Column 3 Value g la 820 205 18. 5 894 2a 1, 075 215 15. 0 1, 149 3a 1, 485 248 12. 5 1, 559 4a 1, 870 311 12. 5 1, 944 5a 2, 230 320 10. 5 2, 304 6a 2, 410 301 9. 0 2, 484 7a 915 228 18. 5 989 841 1,100 224 15. 0 1, 174 9d 1, 460 243 12. 5 1, 534 10a 1, 760 290 12. 5 1, 834 11a 2, 150 307 10. 5 2, 224 12a 2, 215 316 9. 0 2, 289

PART 3 As previously pointed out the present invention is concerned with acidic esters obtained from the diols described in Part 2, preceding, said diols being in turn obtained from oxypropylated monohydric derivatives obtained as described in Part 1, preceding. Said esters, and more-particularly acidic esters, are obtained from various polycarboxy acids, particularly dicarboxy acids such as adipic acid, phthalic acid, or anhydride, succinic acid, diglycollic acid, sebacic acid, azelaic acid, aconitic acid, maleic acid or anhydride, citraconic acid or anhydride, maleic acid or an-' hydride adducts as obtained by the Diels-Alder reaction from reactants such as maleic anhy dride and cyclopentadiene. Such acids should be heat stable so they are not decomposed during esterification. They may contain as many as 36 carbon atoms as, for example, the acids obtained by dimerization of unsaturated fatty acids, unsaturated monocarboxy fatty acids, or unsaturated monocarboxy acids having 18 carbon atoms. Reference to the acid in the hereto appended claims obviously includes the anhydrides or any other obvious equivalents. My preference, however, is to use polycarboxy acids having not over 8 carbon atoms.

The production of esters including acid esters (fractional esters) from polycarboxy acids and glycols or other hydroxylated compounds is well known. Needless to'say, various compounds may be used such as the low molal ester, the anhydride, the acyl chloride, etc. However, for purpose of economy it is customary to use either the acid or the anhydride. ,A conventional procedure is employed. Ona'laboratory scale one can employ a resin pot of the kind described in U. S.

Patent No. 2,499,370, dated March '7, 1950, to De Grotte and Keiser, and particularly with one more opening to permit the use of a porous spreader if hydrochloric acid gas is to be used as a catalyst. Such device or absorption spreader consists of minute alundum thimbles which are connected to a glass tube. One can add a sulfonic acid such as para-toluene sulfonic acid as a catalyst. There is some objection to this because in some instances there is some evidence that this acid catalyst'tends to decompose or rearrange oxypropylated compounds-and particularly'likely to do so if the esterification temperature is too high. In the case of polycarboxy acid such as diglycollic acid, which is strongly acidic there is no need to add any catalyst. The use of hydrochloric gas has one advantage over para-toluene sulfonic acid'and that is that at the end of the reaction it can be removed by flushing out with nitrogen, whereas there is no reasonably convenient means available'of removing the paratoluene sulfonicacid or other sulfonic acid employed. If hydrochloric acid is employed one need only pass the-gas through at an exceedingly slow rate so as to keep the reaction mass acidic. Only a trace ofacid need be present. I have employed hydrochloric acid gas or the aqueous acid itself to eliminate the initial basic -material. My preference, however, is to use no catalyst whatsoever and to insure complete dryness of thediol as described in the final procedure just preceding Table 3.

The products obtained in Part 2 preceding may contain a basic catalyst. 'As a general procedure I have added an amount of half-concentrated hydrochloric acid considerably in excess of what is required to neutralize the residual catalyst. The mixture is shaken thoroughly and allowed to stand overnight. It is then filtered and re-- fiuxed with the xylene present until the water can be separated in a phase-separatingtrap. As soon as the product is substantially free from water the distillation stops. This preliminary step can be carried out in the flask to be used for esterification. If there is any further deposition of sodium chloride during the reflux stage needless to say a second filtration may be required. In any event the neutral or slightly acidic solution of the oxypropylated derivatives described in Part 2 is then diluted further with sufficient xylene, decalin, petroleum solvent, or the like, so that one has obtained approximately .a 65% solution. To this solution there is added a" polycarboxylated reactant as previously described, such as phthalic anhydride, succinic acid or anhydride, diglycollic acid, etc.

dicated-by eliminathnofwater or drop in carboxyl value. Needless-to. say, if oneproduces a halt-ester. from an hydride such. asphthalic anhydride, no .water iseliminated, However, ifit is .obtained from. diglycollic acid,,.for.,-example, Water is eliminated. All such procedures are conventionaland have been sothoroughly describedin the literature that further, consideration will be limitedto afew examples .and a comprehensive table...

Other procedures for eliminating, the basicresidual .catalyst, ifv any, can be,employed.- For example, the oxyalkylation, can be conducted in absence of a solvent orthesolvent removed after oxypropylation. Suchoxypropylation end prode uct can then be acidified with, J'ustenough concentrated hydrochloric acid- .to .just. neutralize .the residual basiocatalyst. To this product onecan then add a small amount ofvanhydrous sodium sulfatelsufiicient in .quantityto take up any water that is present) andthenv subject the mass to centrifugal force so as to eliminate the-hydrated sodium sulfate and probably the sodium. chloride formed. The .clear somewhat viscous straw-col:- or-ed amber liquid-so .obtainedmay contain a small amount of sodium sulfate. orsodium chloride but, in anyevent, is perfectly acceptabl for esterification in themanner described.

Itis to be pointed out-that 1theproducts here described are'not polyesters in .the sense that there is a-plurality of both diol radicals and. acid radicals; the product is characterizedby having only one diolradical.

In some instances: and, in fact, in many instances I havefound that in spite of the .dehydra-. tion methods employed above that a mere trace of water still comes through andthat this mere trace of water. certainly interferes with theacetyl or hydroxyl-value determination, at-leastwhen a number of conventional.procedures are used and may retard esterification, particularly where there is no sulfonic acid or hydrochloricacid present as a catalyst. Therefore-A have. preferredto use the following procedurenl hav employed about 200 grams of -the diol asdescribed in Part 2, preceding; I have added about 60 grams of benzene, and then refluxed thi mixture in theglass resin pot using a phase-separating trap until the benzene carriedv outall the water. present as waterof solution or the equivalent. Ordinarily this refluxing temperature is apt to be in theneighborhood of 130 topossibly 150 C. When all this wateror moisture has'been removed I also with.- draw approximately 20gramsor a little less benzone and then add the required amount of the carboxy reactant and also about 150' grams of a high boiling aromatic petroleum solvent. These solvents are sold by various oil refineries and, as far as solvent efiect-act as if they were almost tillation datain the particular, typeI have em ployed. and, found very satisfactory is the following:

I. B. P., 142 c.- I I 5 ml., 200 0. 55 m1., 244 0. ml, 209 0. 50 ml., 243C. ml-., 215 0. 551111., 252 0. ml., 216 0. 70ml, 252 0. ml., 220 0. '25 ml,, 260 0.

. ml., 225 0. 30 ml., 264 0. m1.,' 230. o. ml., 270 c. 40ml, 2341c. ml., 280?? o. 45 mi, 237C. m1...30v o.

After this material is added, refluxing is continued and, of course, is at a high temperature, to Wit, about to C. If the carboxy reactant is an anhydride needless to sayno water of reaction appears; if the carboxy reactant is anacid water of reaction should appear and should beelimin'ated at the above reaction tem-. perature. If it is not eliminated I simply separate out another 10 or 20 cc. of benzene by means, of the phase-separating trap and thus raise the temperature to or C., or even to 200'C., if need be. My preference is not to go above 200 C.

The use of such solvent is extremely satisfactory provided'one does, not attempt to remove the solvent subsequently except by vacuum distillation and provided there is no objection to a little residue. Actually, when these materials are used for a purposesuch as, demulsification thesolvent might just as Well be allowed to remain. If the solvent is to be removedby distillation, and particularly' vacuum distillation, then the high boiling aromatic petroleum solvent might well be replaced by some more expensive solvent, such as decalin or an alkylated decalin which has a rather definite or close range'boilingpoint. The removal of thesolvent, of course, is purely a conventional procedure and requires no elaboration.

In theappended table Solvent #7-3, which appears in all instances, is a mixture of '7 volumes of. the .aromatic.petroleum solvent previously de..- scribed and 3 volumes of benzene. used, or a similar mixture, in the manner previously described. In a large number of similar examples decalin has been used but it is my preference to usethe above mentioned mixture and particularly with the preliminary step of removing all the Water. If one does not intend to remove the solvent my preference is to use the-petroleum solvent-benzen mixture although 0bviously any of the other mixtures, such as decalin and xylene, can be employed.

The data included in the subsequent tables, 1. e., Tables'3 and 4, are self-explanatory, and very complete and it'is'believed no further elabcompletely aromatic in character. Typical d1s- (30 oratlon is necessary:

TABLE 3 Mol. Wt. Amount Njo. Ex. N o. of of Hydroxy, Hydroxy Amt. of Acid Hydroxy Ompd. by Compound Polycarboxy Rcactant. Used.

Ester Compound 0H Used (grs) e m: (e a).

894: 224; Phthalic Anahydride 74 894 224 v Maleic Anhydride. 49 894 224 Citraconic Anyhdride. 56 894 224 Succinic Anhydride; 50 894 22 4 Diglycollic Acid 67 894 224 Aconitic Acid 87 1,149 230 Phthalic Anhydride 59 l, 149 230 Maleic Anhydride 39 1,1119 L 230' Citraconic Anhydride 45 1, 149 230 Succinic Anhydride 40 l, 149 230 Diglycollic Acid. 54 l, 149 230 Aconitic Acid 70 This was 'mass.

sameprocedure using decalin or a mixture of' decalin or benzene in the same manner and ultimately removed all the solvents by vacuum salt should be eliminated, at least for exploration experimentation, and can be removed by filtering. Everything else being equal as the size of the molecule increases the reactive hydroxyl radical represents a smaller fraction of the entire molecule and thus more difficulty is involved in obtaining complete esterification.

Even under the most carefully controlled conditions of oxypropylation involving comparatively low temperatures and long time of'reaction there are formed certain compounds whose compositions are still obscure. Such side reaction products can contribute a substantial proportion of the final cogeneric reaction mixture. Various suggestions have been made as to the nature of these compounds, such as being cyclic polymers of propylene oxide, dehydration products with the appearance of a vinyl radical, or isomers of propylene oxide or derivatives thereof, i. e., of an aldehyde, ketone, or allyl alcohol. In some instances an attempt to react the stoichiometric amount of a polycarboxy acid with the oxypropylated derivative results in an excess of the carboxylated reactant for the reason that apparently under conditions of reaction less reactive hydroxyl radicals are present then indicated by the hydroxyl value. Under such circumstances there is simply a residue of the carboxylic reactant which can be removed by filtration or, if desired, the esterification procedure can be repeated using an appropriately reduced ratio of carboxylic reactant.

Even the determination of the hydroxyl value and conventional procedure leaves much to be desired due either to the cogeneric materials previously referred to, or for that matter, the presence of any inorganic salts or propylene oxide. Obviously this oxide should be eliminated.

The solvent employed, if any, can be removed from the finished ester by distillation and particularly vacuum distillation. The final products or liquids are generally pale amber to amber in color, and show moderate viscosity. They can be bleached with bleaching clays, filtering chars,

and the like. However, for the purpose of demulsi-fication or the like color is not a factor and decolorization is not justified.

In the above instances I have permitted the solvents to remain present in the final reaction In other instances I have followed the distillation. Appearances of the final products are much the same as the diols-before esterification and in some instances were somewhat darker in color and had a reddish cast and perhaps somewhat more viscous.

PART 4 Previous reference has beenmade to the fact that diols such as polypropyleneglycol of approximately 2,000 molecular weight, for example, have been'esterified with dicarbox'y 'acids and employed as demulsifying agents. :On first ex-r,

amination the difference between-thehereinxde- :scribed productsand such comparable products appears to be rather-insignificant.- In--fact,'the

difference is such that it fails to explain the sify faster andtgive cleaner oilin many-instances.

. The method of making such' comparative I tests propylene glycols indicated as RO(C2H40)3OH.

has been described in a'booklet entitled Treating Oil Field Emulsions, used in the Vocational Training Course, Petroleum Industry Series, of the American Petroleum Institute.

The difference, of course, does not reside in'the carboxy acid but in the diol. Momentarily an effort will be made to emphasize certain things in regard to the structure of a polypropyleneglycol, such as polypropylene glycol of a-2000m,olecular weight. Propylene glycol has a. primary alcohol radical and a secondary alcohol radical. In this sense the building unit which forms polyis not symmetrical. Obviously, then, polypropylene glycols can be obtained, at least theoretically, in which two'secondary alcohol groups are unitedor a secondary alcohol group is united to a primary alcohol group, etherization being involved, of 'coursem'n each instance.

Usually no effort is made to differentiate between oxypro'pylation' taking place, for example, at the primary alcohol unit radical or' the secondary alcohol radical. Actually, when such products are obtained, such as a high 'molal polypropylene glycol or the products obtained in the manner herein described one does not obtain a single derivative such as HO(RO)11H in which n has one and only one value, for instance, 14,15 or 16, or the like. Rather, one obtains a cogeneric mixture of closely related or touching homologues. These materials invariably have high molecular weights and cannot be separated from one another by any known procedure without decomposition. The properties of such mixture represent the contribution of the various individual members of the mixture. 'On a statistical basis, of course, '11. can be appropriately readily obtain or or %of such compound. However, in the case of at least monohydric initial reactants one can readily draw the formulas of a large number of compounds which appear in some of the probable 'mixtures or can be prepared as components and mixtures which are manufactured conventionally.

Simply by way of illustration reference is made to the copending application of De Groote, Wirtel and Pettingill, Serial No. 109,791, filed August 11,

1949 (now Patent No. 2,549,434, dated April l'l,

However, momentarily referring again to a 'monohydric initial reactant it is obvious that" if one selects any such:simple hydroxylated'compound and subjects such compound to oxyalkylation, such as oxyethylation, or oxypropylation, it becomes obvious that one is really producing a polymer of the alkylene oxides except forthe terminal group. This is particularly true where-the amount of oxide added is comparatively large,'for

instance, 10, 20, 30, 40, or 50 units. If such compound is subjected to oxyethylation so as to introduce 30 units of ethylene oxide, it is well known that one does not obtain a single constituent which, for the sake=of convenience, may be Instead, one Ohtainsa cogeneric mixture ofclosely related -homologues, in which the formula maybe shownas the following, R0 (CZHdO) nHfiwhereinn, as far 75 as the statistical average goes,--is '30 ,"butthe 1ndivldual members present in significant amount may vary from instances where n has a value of 25, and perhaps less, to a point where 71. may represent 35 or more. Such mixture is, as stated, a cogeneric closely related series of touching homologous compounds. Considerable investigation has been made in regard to the distribution curves for linear polymers. Attention is directed to the article entitled Fundamental principles of condensation polymerization, by Flory, which appeared in Chemical Reviews, volume 39, No. 1, page 137.

Unfortunately, as has been pointed out by Flory and other investigators, there is no satisfactory method, based on either experimental or mathematical examination, of indicating the exact proportion of the various members of touching homologous series which appear in cogeneric condensation products of the kind described. This means that from the practical standpoint, i. e., the abilityto describe how to make the product under consideration and how to repeat such production time after time without difiiculty, it is necessary to resort to some other method of description, or else consider the value of n, in formulas such as those which have appeared previously and which appear in the claims, as representing both individual constituents in which 12 has a single definite value, and also with the understanding that n represents the average statistical value based on the assumption of completeness of reaction.

This may be illustrated as follows: Assume that in any particular example the molal ratio of the propylene oxide to the glycerol diether is to 1.. Actually, one obtains products in which n probably varies from 10 to 20, perhaps even further. The average value, however, is 15, assuming, as previously stated, that the reaction is complete. The product described by the formula is best described also in terms of method of manufacture.

However, in the instant situation it is obvious that there is a distinct difierence of structure between the initial diol subjected to reaction with polycarboxy acids and an ordinary polypropyleneglycol such as polypropylene glycol 2000. In the case of the last mentioned compound the two hydroxyls are in the alpha-omega position to each other, i. e., attached to opposite terminal carbon radicals and there is no terminal branched radical such as Stated another way, looking upon the ordinary glycol molecule as having two branches extended from a center or central part of the molecule in the present instance, 1. e., the reactant herein employed as initial raw material, one has four branches of the molecule, i, e., the two hydroxyl radicals at one terminal and the branched radical as previously described at the other terminal. Furthermore, in the case of the instant diol instead of the hydroxyl radicals being in an alphaomega position to each other they are terminally attached to two of the three terminally adjacent carbon atoms, being the terminal group opposite All of this has been pointed out previously in the formulas which illustrate the herein specifiedglemulsifying agents. 1

PART 5 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil,'cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, prcpyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be"em ployed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of process may be admixed with one or more of the solvents customarily used in connec tion with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable Wellknown classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

In practicing my process for resolving petroleum emulsions of the water-in-oil type, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used, alone or in combinationwith other de. mulsifying procedure, such as the electrical dehydration process.

One type of procedure is to accumulate a volume of emulsified oil in a tank and conduct a batch treatment type of demulsiflcation procedure to recover clean oil. In this procedure the emulsion is admixed with the demulsifier. for example by agitating the tank of emulsion and slowly dripping demulsifier into the emulsion; In some cases mixing is achieved by heating the emulsion while dripping in the demulsl fier, depending upon the convection currents in the emulsion to produce satisfactory admixture.

In a third modification of this type of treatment, a circulating pump withdraws emulsion from, e. g., the bottom of the tank, and reintroduces it into the top of the tank, the demulsifier being added, for example, at the suction side of said circulating pump.

In a second type of treating procedure, the demulsifier is introduced into the well fluids at the well-head or at some point between the wellhead and the final oil storage tank, by means of an adjustable proportioning mechanism or proportioning pump. Ordinarily the flow of fluids through the subsequent lines and fittings sufiices to produce the desired degree of mixing of demulsifier and emulsion, although in some instances additional mixing devices may be introduced into the flow system. In this eneral 23'? procedure, the system may include various mechanical devices forv withdrawing free water, separating entrained water, or accomplishing quiescent settling of the chemicalized emulsion. Heating devices may likewise be incorporated in any. of the treating procedures described herein.

A third type of application (down-the-hole) of demulsifier to emulsion is to introduce the demulsifier either periodically or continuously in diluted or undiluted form into the well and to allow it to come to the surface with the well fluids, and then to flow the chemicalized emulsion through any desirable surfacev equipment, such as employed in the other treating procedures. This particular type of application is decidedly useful when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

'In all cases, it will be apparent from the foregoing description, the broad process consists simplyv in introducing a. relatively. small proportionof demulsifier into a relatively large proportion-of, emulsion,- admixing the chemical and emulsion either. through natural flowor' through specialiapparatus, with or without the application of heat, andallowing the mixture to stand quiescent until the undesirable water contentof. the emulsion separatesand settles from the mass.

The following. is a typical installation.

A, reservoir. to hold the. demulsifier. of the kind described, (diluted or undiluted) is placedatthe well headnwhere the eiiiuent liquids. leave the well; 'Thisv reservoir, or. container, which may vary froml' gallons t0 50 gallons for. convenience, is connected to a proportioning pumpwhich injects the demulsifier drop-wise into the fluids leavingthe well. Such chemicalized fluids pass throughthefflowlinejinto asettling tank. The settling tank. consists" of i a tank. of any convenient size, forinstance,v one which will hold amounts ofjfiuidproduced inA to 24 hours (500' barrelsflto 200'0 barrels capacity), and in which there. is a perpendicular conduit from the top of'thetank to almost the very bottom .so asto, permitthe incoming'fluids to pass from the top of the settling tank to the bottom,.so that such incoming, fluids do not disturb stratification which takes place during the course of demulsifi'cation. ,The settling tank'has twooutlets; one being 'belowthe water level to drain offthe. water. resulting, from demulsification or, accompanying. the emulsion as free water, the other being anoil outlet: atthe topv to permit the passage-of dehydrated; :oil to a .second tank,-beinga.=storagetank,'which holds pipeline or. dehydrated oil. If desired,-the conduit'. or pipewhichserves to carry the" fluids from the well to thesettling tank may include a: sectionv of. pipe with baffles to serve as a mixer, to insure. thoroughdistribution ofthe demulsifier throughout the-fluids, or aheaterfor raising the temperature of the fluids to-some convenient temperature, for instance, 120to l60-F or: both heater and mixer.

Demulsificationprocedure: is started-:- by. simply settingthaptunp seas to-iee'd. a comparativelylarge. ratio-of-demulsifler; for instance, 11.52600; Assoon as: av complete break-i or satisfactorydemulsification .isobtained the pump is: regu= lated untilwexperience shows that the amount of demulsifier beingaddedzis just suiflcient' to..produceclean or dehydrated 0131; The amountb'eing fed at such stagefis:usuallyalxwflw,1115;000; ;-29 199.orthei11se.-5

Inrmany. instances the oxyalkylated, products" herein specified as demulsifiers can be conven iently used. without dilution. However, as previ ously. noted; they may: be diluted as' desired;.vvith.

any-suitable solvent. For instance, bymixing-75 parts; by; weight of an oxyalkylated derivative;

for example, the product of Example 290 with 15 parts byt weight of. xylene and 10 parts by'weight of; isopropyl alcohol, an excellent demulsifier obtained. Selection: ofthe-solvent will vary,.de-;-

pending'upon, the solubility characteristics-oithez oxyalkylated product, and of course willbe' dictat'edin part by economic considerations; i. e., cost.

As notedabove, the; products herein described maybe used notonly indiluted form, butalso; may be usedadmixedw-ithsome other chemical demulsifier.

PART 6 Previous reference has been made to other oxyalkylating agentsother than propylene oxide,

such as ethylene oxide. Obviously variants can be prepared which do. not depart from what is. The. diol"derived' by etherization of glycerol, in the. V manner, describedcan beprepared from glycerol, diethers. which have been reacted with ethylenev saidherein but do produce modifications.

oxide in modest amounts and then subjectedto.

oxypropylationv provided that the resultant dea More specifically then-one mole of suchetherized glycerol of: the kind described can-be prepared irom onemole of a'glycerol diether which has been treated with2, 4 or- 6 moles ofethylene oxide-andthen treated with propylene oxide so as to produce awater-insoluble, kerosene-soluble diol-inwhich there are. present 15' to; oxide radicals; asvpreviously specified. Similarly the: propylene: oxide-can beadded first and then the ethylene oxide; or'random oxyalkylation: can be employed .usinga mixture of thetwo oxides; The compoundsjso. obtained are readily esterified in the 'samemanner' as described in Part 3, preced ing. Incidentally, the diols described in Part2 or the modifications described therein can be treated with various reactants such as glycide, epichlorohydrin, dimethyl sulfate, sulfuric acid, maleic anhydride, ethylene imine, etc. If treated with .epichlorohydrin or monochloroacetic acid: the resultant'product can befurther-reacted, with a tertiary; amine'such-aspyridine, or the likeato give quaternary ammonium compounds. If treatedwithmaleic anhydride. to give a total ester the resultant can be treated with sodium: bisulfiteto; yield a ,sulfosuccinate. Sulfo groups'can be: introduced also by means-of asulfating agent as previously suggested, or by treating the: chloroaceticiacid resultant with sodium sulfite.

Ihave. found that if such hydroxylated'compoundor compounds are reacted further-seas to produceentirely new'derivatives, such new derivatives have the properties. of the original hydroxylated compound insofar that they are effective and valuable demulsifying agents for resolution of water-in-oil emulsions as found in the petroleumindustrmas break inducersin doctor treatmentofsourcrude,.etc.

Having thus described my invention, what l.

Other variantsclaim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including hydrophile synthetic products; said hydrophile synthetic products being characterized by the following formula:

in which n is a whole number varying from 15 to 80; n is a Whole number not over 2; R is a hydrocarbon radical having less than 8 carbon atoms, and R is the radical of the polycarboxy acid ooomn' in which n has its previous significance; with the further proviso that the parent diol prior to esterification be water-insoluble and kerosenesoluble, and furthermore that in said diol the two hydroxyl radicals be attached to two of the three adjacent carbon atoms of a terminal group opposite to the terminal group CaHsO 2. .A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including hydrophile synthetic products; said hydrophile synthetic products being characterized by the following formula:

OHsCs(0HgCa) OC3H5 0 OR 4% H H il Ho0o ,.-R o-o-o c-o R(OOOH)..' H H H in which n is a whole number varying from 15 to 80; n is a whole number not over 2; R is a hydrocarbon radical having less than 8 carbon atoms, and R is the radical of the polycarboxy acid /COOH in which n has its previous significance; said polycarboxy acid having not more than 8 carbon atoms; with the further proviso that the parent diol prior to esterification be water-insoluble and kerosene-soluble, and furthermore that in said diol the two hydroxyl radicals be attached to two of the three adjacent carbon atoms of a terminal group opposite to the terminal group CaHt 3. A process for breaking petroleum emulsions 26 of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including hydrophile synthetic products; said hydrophile synthetic products being characterized by the following formula:

in which n is a whole number varying from 15 to R is a hydrocarbon radical having less than 8 carbon atoms, and R is the radical of the dicarboxy acid COOH COOH said dicarboxy acid having not more than 8 carbon atoms; with the further proviso that the parent diol prior to esterification be water-in soluble and kerosene-soluble, and furthermore that in said diol the two hydroxyl radicals be attached to two of the three adjacent carbon atoms of a terminal group opposite to the terminal group 4. The process of claim 3 wherein R. has at least 3 carbon atoms.

5. The process of claim 3 wherein R has at least 3 carbon atoms and is derived from a watersoluble alcohol.

6. The process of claim 3 wherein R has at least 3 carbon atoms, is derived from a watersoluble alcohol, and the dicarboxy acid is phthalic acid.

7. The process of claim 3 wherein R. has at least 3 carbon atoms, is derived from a watersoluble alcohol, and the dicarboxy acid is maleic acid.

8. The process of claim 3 wherein R. has at least 3 carbon atoms, is derived from a Watersoluble alcohol, and the dicarboxy acid is suc cinic acid.

9. The process of claim 3 wherein R has at least 3 carbon atoms, is derived from a watersoluble alcohol, and the dicarboxy acid is citraconic acid.

10. The process of claim 3 wherein R. has at least 3 carbon atoms, is derived from a watersoluble alcohol, and. the dicarboxy acid is diglycollic acid.

MELVIN DE GROOTE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,507,560 De Groote et a1. May 16, 1950 2,514,399 Kirkpatrick et a]. July 11, 1950 2,562,878 Blair Aug. 7, 1951 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING HYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING CHARACTERIZED BY THE FOLLOWING FORMULA: 